CN106117514A - Difunctionality base epoxy and monofunctional primary amine and/or difunctionality base secondary amine hardener mixture are as the purposes of prepreg - Google Patents
Difunctionality base epoxy and monofunctional primary amine and/or difunctionality base secondary amine hardener mixture are as the purposes of prepreg Download PDFInfo
- Publication number
- CN106117514A CN106117514A CN201510217836.1A CN201510217836A CN106117514A CN 106117514 A CN106117514 A CN 106117514A CN 201510217836 A CN201510217836 A CN 201510217836A CN 106117514 A CN106117514 A CN 106117514A
- Authority
- CN
- China
- Prior art keywords
- difunctionality base
- purposes
- mixture
- difunctionality
- prepreg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
The present invention provides the mixture purposes as prepreg of a kind of difunctionality base epoxy and monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent, and it is used for being impregnated with different materials, forms thermoplastic composite；And a kind of thermoplastic composite and the method for preparation.
Description
[technical field]
The present invention is the purposes about a kind of mixture, and a kind of mixture using difunctionality base epoxy and monofunctional primary amine and/difunctionality base secondary amine sclerosing agent is as the purposes of prepreg, thermoplastic composite and the method preparing it.
[prior art]
Material is the mother of industry, and composite (Composite Materials) is then the main flow of material industry in modern age.Composite has the characteristics such as intensity height, light weight, acid and alkali-resistance, resistance to weather, assembles the advantage of various material, the most gradually replaces traditional metal material, ceramic material, even general macromolecular material, is widely used in various industry.
Composite is a kind of multiphase solid material of two or more physics combinations of substances different with chemical property, and in composite, generally has a continuous phase, referred to as base material；Another phase is dispersion phase, referred to as reinforcing material.
And composite can be divided into polymer composite (Polymer Matrix Composite) according to the difference of its base material；Carbon/carbon compound material (Carbon/Carbon composites)；Metal-base composites (Metal Matrix Composites, MMC)；Ceramic matric composite (Ceramic Matrix Composites, CMC) etc..Dispersion phase in composite, then according to the difference of reinforcing material, can be divided into filamentary composites, granular composite material, long-pending laminar composite, flake composite or fill shape composite etc..
Wherein, the macromolecule resin fibrous composite of high-strength light weight attracted most attention in recent years, and had started to substantial amounts of substituted metal alloy product, and yield and application the most constantly expand, and was widely used in industries such as automobile, electronics, electric, building materials.
And it is divided into heat curing-type composite wood and thermoplastic shape composite wood two system according to macromolecule resin base material.The thermoplastic composite that thermoplastic resin base material combines reinforcing material made has many advantages, such as: toughness is high, resistance to impact is good, prepreg is stable, without storing time restriction, the manufacturing cycle is short, chemical-resistance good, hydroscopicity is low, repeatable processing etc..Additionally, it possesses high efficiency form processing and the two big advantages such as finished product is recyclable on processing procedure, therefore compared with the favor of the heat curing-type composite wood person that is more subject to processing processing procedure on using.
The manufacture method of the thermoplastic composite wood of main flow is hot melt (also known as melted impregnation method) or solvent method the most on the market；Melted impregnation method be resin is added heat fusing after, reinforcing material is completed impregnation by melted resin；Solvent method is to use solvent to be completely dissolved by resin, changes or reduces thermoplastic resin kenel (being turned liquid by solid-state) at normal temperatures and viscosity, and be impregnated with reinforcing material with this, again by solvent volatilization after being impregnated with.
[summary of the invention]
Although the known technology being correlated with can prepare thermoplastic composite material, but solvent method uses a large amount of organic solvent on processing procedure, discharges a large amount of organic volatile and easily causes environmental pollution；Hot melt rule is poor with the impregnation of reinforcing material (or claiming dispersion phase), easily causes composite finished product intralayer defects.Additionally, at present thermoplastic composite is faced and maximum has a problem in that thermoplastic resin melt temperature height, viscosity are the highest, therefore have there is sizable difficulty preparing prepreg.
For solving the problems referred to above, the present invention utilize epoxy resin to mix with amine type hardeners after the characteristic of low-viscosity, allow resin under the use being not required to solvent, and not yet solidify, i.e. first effectively it is impregnated with reinforcing material, then carries out in-situ polymerization, form thermoplastic composite.
And the present inventor is found surprisingly that, generally and multi-functional yl amine forms thermosetting resin to be different from known difunctionality base epoxy, the present inventor uses monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent, difunctionality base epoxy is made to form thermoplastic resin, and for thermoplastic composite, there are preferably processing procedure and effect, and the difunctionality base epoxy used can the direct in-situ polymerization when being impregnated with dispersion phase, that is this difunctionality base epoxy can first be impregnated with, it is polymerized under the state that dispersion phase has been impregnated with afterwards, from without with the presence of the problem being difficult to be impregnated with in the past.
Therefore, present invention is primarily targeted at the mixture purposes as prepreg of a kind of difunctionality base epoxy of offer and monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent, it is used for being impregnated with in-situ polymerization after fiber, forms thermoplastic composite.
In a preferred embodiment, in this difunctionality base epoxy, containing the epoxy resin composition of one or more 60 to 100wt%, and containing the functional interpolation auxiliary agent of 0～25wt%.
In another preferred embodiment, this difunctionality base epoxy is that epoxide equivalent (EEW) is between 50 to 650 persons.
In another preferred embodiment, this difunctionality base epoxy is for comprising arbitrary or mixing following formula (I) to (IV):
Wherein, X1Represent C4～C18Alkyl；N is 0～20；X2To X21Can be identical or different, and represent H, P, alkyl or halogen；And Y represents S, O or C atom.
In a further advantageous embodiment, this monofunctional primary amine level/or difunctionality base secondary amine sclerosing agent comprise one or more than one functional group's primary amine levels/or difunctionality base secondary amine mixture, the functional interpolation auxiliary agent of 0～10wt% of 80～100wt%.
In a further advantageous embodiment, this functional interpolation auxiliary agent selects the group that free shrinking agent, flame retardant, ultraviolet resistance auxiliary agent, anti-wear agent and toughener are formed.
In a further advantageous embodiment, this monofunctional primary amine level/or difunctionality base secondary amine sclerosing agent are for comprising arbitrary or mixing following formula V to (VII):
Wherein, RaFor alkyl, aryl or aralkyl；RbFor alkyl or aryl；RcFor alkyl.
Another object of the present invention is to provide a kind of method preparing thermoplastic composite, comprise: mixing difunctionality base epoxy forms prepreg with monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent, and this mixture is impregnated with in-situ polymerization after a dispersion phase.
In a preferred embodiment, this prepreg impregnation dispersion phase is through hand lay-up, brushwork forming or priming by vacuum mode, can also use the processing mode impregnation dispersion such as known drum type coiling method (Drum Winding) and the hot melt impregnation processing procedure fiber reinforced composite material such as (Hot-melt Impregnation) to, more heated carry out in-situ polymerization.
In a preferred embodiment, when this mixture is low-viscosity, prepreg impregnation dispersion phase is through drum type coiling method (Drum Winding), more heated carries out in-situ polymerization.
In a preferred embodiment, when this mixture is high viscosity, prepreg impregnation dispersion phase is through high temperature impregnation processing procedure (Hot-melt Impregnation) impregnation, more heated carries out in-situ polymerization.
Another object of the present invention is to provide a kind of thermoplastic composite, it makes to prepare in aforementioned manners.
Difunctionality base epoxy and monofunctional primary amine and/or the purposes of mixture, the method preparing thermoplastic composite and this composite of difunctionality base secondary amine sclerosing agent according to the present invention, it is as follows compared to the advantage that prior art produces: the present invention does not uses volatile material, the most relatively environmental protection；Make without attrition grinding or thin film, relatively save the energy；Thermoplastic composite low temperature can be impregnated with less than 60 degree, and therefore processing procedure is easier to；And due to properties of materials so that composite interlayer associativity is preferable；Thermoplastic composite has the characteristics such as resistance to combustion, endurance, impact resistance, resistance to yellow, therefore can be applicable to multiple fields.
[brief description of drawingsfig]
Fig. 1 is to observe thermoplastic carbon fibre initial rinse fabric vertical section with optical microscope FS-105 (100x enlargement ratio), is a) to be impregnated with carbon fiber vertical section with PKHH with hot melt (200 DEG C), and its fibrous inside local presents dry yarn state；B) by being impregnated with carbon fiber vertical section with embodiment 1, its fiber presents complete wetting；C) by being impregnated with carbon fiber vertical section with embodiment 4, its fiber presents complete wetting；D) with embodiment 5 impregnation carbon fiber vertical section, its fiber presents complete wetting.
[embodiment]
The terms " one " or " a kind of ", when being used in conjunction in claim or description with " comprising ", may represent and have one, but also comply with " one or more " or " at least one ".
The difunctionality base epoxy of the present invention and monofunctional primary amine and/or the purposes of the mixture of difunctionality base secondary amine sclerosing agent
One of the main object of the present invention is the mixture providing a kind of difunctionality base epoxy and monofunctional primary amine and/or the difunctionality base secondary amine sclerosing agent purposes as prepreg, it is in-situ polymerization after impregnation one dispersion phase, forms thermoplastic composite.
Term " prepreg " referred to herein refers to the leaching material not yet solidified of the dispersion phase (such as fiber, granule, lamination, thin slice or implant) for being impregnated with in composite, and it is the mixture but this difunctionality base epoxy not yet solidification person formed with monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent by mixing difunctionality base epoxy.
Herein referred term " dispersion phase " refers to the material that the difunctionality base epoxy with the present invention and monofunctional primary amine and/or the mixture physics of difunctionality base secondary amine sclerosing agent and chemical property differ, can be referred to as " reinforcing material " again, the example of this dispersion phase can be for fibrous material, granular materials, laminated material, sheeting or packing material, the most preferably fibrous material.
In the purposes of the present invention, wherein in this difunctionality base epoxy, containing the epoxy resin composition of one or more 60 to 100wt%, and containing the functional interpolation auxiliary agent of 0～25wt%.
In the purposes of the present invention, wherein this difunctionality base epoxy is preferably epoxide equivalent (EEW) between 50 to 650 persons, and more preferably 150 to 650.
In the purposes of the present invention, wherein this difunctionality base epoxy is for comprising arbitrary or mixing following formula (I) to (IV):
Wherein, X1Represent C4～C18Alkyl；N is 0～20；X2To X21Can be identical or different, and represent H, P, alkyl or halogen；And Y represents S, O or C atom.
Above-mentioned difunctionality base epoxy can be but be not limited to: bisphenol A type epoxy resin (DGEBA), tetrabromobisphenol A type epoxy resin (NPEB-340), bisphenol f type epoxy resin (DGEBF), resorcinolformaldehyde resin etc..
In the purposes of the present invention, this monofunctional primary amine level/or difunctionality base secondary amine sclerosing agent wherein comprise one or more than one functional group's primary amines and/or the difunctionality base secondary amine mixture of 80～100wt%, the functional interpolation auxiliary agent of 0～10wt%.
In the purposes of the present invention, the viscosity of this mixture is preferably at 25 DEG C, between 100-8000cps, and more preferably 120 to 400cps, most preferably 100 to 150cps.
In the purposes of the present invention, wherein this functional interpolation auxiliary agent selects the group that free shrinking agent, flame retardant, ultraviolet resistance auxiliary agent, anti-wear agent and toughener are formed.Much more the kind of additive is described in known techniques, but actual selection just can must obtain with consumption on the benchmark of experiment.
In the purposes of the present invention, wherein this monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent are for comprising arbitrary or mixing following formula V to (VII):
Wherein, RaFor alkyl, aryl or aralkyl；RbFor alkyl or aryl；RcFor alkyl.
Above-mentioned primary amine and/or difunctionality base secondary amine sclerosing agent, such as fatty amine or aromatic amine, wherein preferably RaTo RcIt is represented as C1To C10Short-chain alkyl, C6To C8Aryl, C7To C19Aralkyl, more preferably benzene methanamine, n-butylamine, diethylene diamine etc..
The method preparing thermoplastic fibre composite of the present invention
Another object of the present invention is to provide a kind of method preparing thermoplastic composite, comprise: mixing difunctionality base epoxy forms prepreg with monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent, and this mixture is impregnated with in-situ polymerization after a dispersion phase.
The method of the present invention is to mix uncured difunctionality base epoxy mixing monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent formation prepreg, difunctionality base epoxy is utilized after mixing, to reduce the characteristic of viscosity with sclerosing agent, effectively can be impregnated with dispersion phase, then, in-situ polymerization makes the resin generation polyreaction of this mixture, forms thermoplastic composite.
After herein referred term " effectively impregnation " refers to mix uncured difunctionality base epoxy mixing monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent formation prepreg, after being impregnated with dispersion phase, the difunctionality base epoxy after solidification can uniformly be combined with dispersion phase afterwards；Visual means, the difunctionality base epoxy of visible about more than 90% can uniformly be combined with dispersion phase, the difunctionality base epoxy of preferably from about more than 95% can uniformly be combined with dispersion phase, and the difunctionality base epoxy of more preferably more than 98% can uniformly be combined with dispersion phase.
In-situ polymerization in the present invention refers to that uncured difunctionality base epoxy, when being the most effectively impregnated with dispersion phase, directly solidifies；The requirement of employing situ aggregation method is: monomer polymerization speed is fast, reacts easily controllable.And in the present invention, in-situ polymerization is to utilize that the initial molecular weight of monomer is little, viscosity is low and the feature of good fluidity, makes dispersion phase wherein be impregnated with monomer, the most directly solidifies.The condition (such as temperature, time etc.) of this solidification can adjust according to different resins and sclerosing agent, but it is preferably interim elevated cure, such as at 30～60 DEG C about one hour, then at 80 to 100 DEG C about one hour, finally within about two hours, solidify at 110 to 140 DEG C, it is preferably with at 30 DEG C about one hour, then at 100 DEG C about one hour, finally little solidifies at present with at 120 DEG C about two；Or, can at 30～60 DEG C about half an hour, then within about two hours, solidify at 140～180 DEG C, be preferably with about half an hour at 50 DEG C, then within about two hours, solidify at 160 DEG C.
The dispersion phase used in the method for the invention, preferably one fibrous material, and the reinforcing fiber that this fibrous material preferably length-width ratio is more than 100 (more preferably more than 1000).Alternatively, it is also possible to use reinforcing fiber fabric (reinforcing fiber fabric, reinforcing fiber compile thing, reinforcing fiber fabric, reinforcing fiber non-woven fabrics etc.).Through reinforcing fiber, the strengthening fabric of the length-width ratio using more than upper numerical value, the reinforcement degree of thermoplastic resin can be improved, produce the fibrous composite of the mechanical property with excellence.
The inorfils such as the organic fiber such as carbon fiber, aramid fiber or glass fibre such as can be used, it is preferable to use carbon fiber as reinforcing fiber.
The fiber filament diameter used as reinforcing fiber can be about 3 to 23 μm, and be possible not only to use as the kind of the glass of glass fibre and be particularly useful as the E glass of reinforcing fiber, S glass, C glass, A glass etc. can also be used, have no particular limits.Filament of glass fiber can be circular, it is also possible to is ellipse etc., is not particularly limited.
Form as glass fibre, it is possible to use the chopped fiber such as glass fibre fulling milling fiber, the long fibre such as fibre glass roving, glass fiber yarn etc..Additionally, glass fibre can also carry out surface process with surface conditioning agents such as silane couplers.
In the method for the invention, wherein this prepreg impregnation discrete state material is through hand lay-up, brushwork forming or priming by vacuum mode.Hand lay-up is to use manual work, i.e. in the reinforcing material laid or dispersion phase (reinforcing material such as: fibrous material), sticks with paste resin with hands until the thickness of required plastic, then obtains thermoplastic composite material by solidifying；Brushwork forming then can either manually or mechanically operation, in the reinforcing material laid or dispersion phase (reinforcing material such as: fibrous material), brushing resin, until the thickness of required plastic, then obtains thermoplastic composite material by solidifying；Priming by vacuum rule is as used one-side mould, die surface glass fibre and the vacuum bag of sealing or vacuum film cover, glass fibre confined space evacuation from mould, then utilizes vacuum pressure to make resin penetrate and soaks fibrous material, treats resin and fiber solidifying postforming afterwards.
It addition, when mixture impregnation fibrous material, it is possible to use known method, manufacture the mixture being mixed formed prepreg and fibrous material by difunctionality base epoxy with monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent.The reinforcing fiber used is not when having this two-dimensional shapes of reinforcing fiber fabric, and mixture prepares through stirring mixing after the reinforcing fiber of interpolation chopped fiber shape in uncured resin, then can solidify in situ.
In a preferred embodiment, when this mixture is low-viscosity, prepreg impregnation dispersion phase is through drum type coiling method (Drum Winding), the most heated in-situ polymerization that carries out, wherein, term " low-viscosity " indication preferred viscosity scope is 50, below 000cps, it is preferably k value 10, below 000cps, most preferably below 500cps.
In a preferred embodiment, when this mixture is high viscosity, prepreg impregnation dispersion phase is through high temperature impregnation processing procedure (Hot-melt Impregnation) impregnation, the most heated carry out in-situ polymerization, wherein term " high viscosity " indication preferred viscosity scope is 50, more than 000cps.
Mixture can contain uncured resin and reinforcing fiber as essential component, it is also possible to adds the shrinking agent as functional interpolation auxiliary agent, flame retardant, ultraviolet resistance auxiliary agent, wear-resisting skill, toughener etc..
Owing to producing polyreaction in the presence of reinforcing fiber and arbitrary adding ingredient, thus generate fibre-reinforced to have thermoplastic plastics be the plastics formed compounded with reinforcing fiber and any adding ingredient in having thermoplastic plastics.Being additionally, since the resin before making macromolecule quantify to compare with the situation of reinforcing fiber, the adaptation of the interface with thermoplastic plastics and reinforcing fiber is good, and the mechanical property (shear strength, impact strength etc.) of product is excellent.
The manufacture method of the invention described above, in the mixture that will obtain in mixed processes injects the mould of desired shape, or by hand lay-up (hand-mold process (hand lay up)) etc. by after laminated for the material of regulation viscosity, by entirety heating etc. is produced polyreaction, thermoplastic fibre composite can be formed, so with large-scale products formed, complicated shape article shaped as representative, variously-shaped article shaped can be manufactured easily and without defect.Further, since before making uncured resin macromolecule quantify, add reinforcing fiber, so reinforcing fiber state with abundant moistening can carry out polyreaction in uncured resin.Therefore, the fibre-reinforced thermoplastic not damage strengthening fiber of gained, the generation in the space can being adequately suppressed in thermoplastic and reinforcing fiber interface.
Can near room temperature (such as through the thermoplastic fibre composite prepared by said method, 20 to 90 DEG C) demonstrate the mechanical property identical with the composite using resin as substrate resin, at high temperature (the most such as, more than 100 DEG C) under easily liquefy, can obtain carrying out 2 processing or the thermoplastic fibre composite reused, recycle.
The thermoplastic fibre composite of the present invention
Another object of the present invention is to provide a kind of thermoplastic fibre composite, it is to make to prepare with the aforedescribed process.
Hereinafter, the preferred embodiment of the invention is described in more detail, but the present invention is not limited to these embodiments.
Embodiment 1
Stir after mixing with benzene methanamine 27.1g with bisphenol A type epoxy resin (DGEBA, EEW=176～184) 95.0g.In 2 hours, in the way of hand laying by resin combination uniform application on 3K carbon cloth, more all press with 50 DEG C of rollers.With 50 DEG C (1 hours), then 100 DEG C (1 hour), last 150 DEG C (2 hours) solidify, and i.e. obtain thermoplastics type's composite.
Embodiment 2
Stir after mixing with triethyl phosphate 1.5g with bisphenol A type epoxy resin (DGEBA, EEW=176～184) 21.0g, n-butylamine 4.1g.In 2 hours, in the way of hand laying by resin combination uniform application on 3K carbon cloth, more all press with 50 DEG C of rollers.With 50 DEG C (1 hours), then 100 DEG C (1 hour), last 150 DEG C (2 hours) solidify, and i.e. obtain thermoplastics type's composite.
Embodiment 3
Stir after mixing with maleic acid 0.6g with bisphenol A type epoxy resin (DGEBA, EEW=176～184) 50.0g, diethylene diamine 11.46g (being dissolved in 2g methanol).In 2 hours, in the way of hand laying by resin combination uniform application on 3K carbon cloth, more all press with 50 DEG C of rollers.With 50 DEG C (1 hours), then 100 DEG C (1 hour), last 120 DEG C (2 hours) solidify, and i.e. obtain thermoplastics type's composite.
Embodiment 4
(having mixed at 25 DEG C, viscosity is 4000-8000cps) with tetrabromobisphenol A type epoxy resin (NPEB-340, EEW=340-360) 50.0g, after being heated to 120 DEG C, it is mixed and stirred for uniformly with 8.12g benzene methanamine.Afterwards within half an hour with hand laying uniform application on 3K carbon cloth, more all press with 100 DEG C of rollers.With 80 DEG C (half an hour), then 160 DEG C (2 hours) solidify after carrying out, and i.e. obtain thermoplastics type's carbon fibre composite.
Embodiment 5
With bisphenol f type epoxy resin (DGEBF, EEW=170-174) 50.0g, it is mixed and stirred for uniformly (having mixed viscosity at 25 DEG C is 120-300cps) with 15.75g benzene methanamine.Afterwards within half an hour with hand laying uniform application on 3K carbon cloth, more all press with 50 DEG C of rollers.With 50 DEG C (half an hour), then 160 DEG C (2 hours) solidify after carrying out, and i.e. obtain thermoplastics type's carbon fibre composite.
Embodiment 6
With resorcinolformaldehyde resin (EEW=111.12) 50.0g, it is mixed and stirred for uniformly (having mixed viscosity at 25 DEG C for 120-300cps) with 24.11g benzene methanamine.All press with 50 DEG C of rollers again on 3K carbon cloth with hand laying uniform application within half an hour afterwards.With 50 DEG C (half an hour), then 160 DEG C (2 hours) solidify after carrying out, and i.e. obtain thermoplastics type's carbon fibre composite.
Comparative example
Illustrate in the lump with reference to Fig. 1.
Relatively thermoplastic resin PKHH (InChem Co.) makes thermoplastic carbon fibre initial rinse fabric with the present invention (embodiment 1,4,5) with hot melting way impregnation, thermoplastic carbon fibre initial rinse fabric (3K, FAW=200) vertical section is as shown in Figure 1, thermoplastic carbon fibre initial rinse fabric vertical section is observed with optical microscope FS-105 (100x enlargement ratio), Fig. 1 a) it is that PKHH is impregnated with carbon fiber vertical section with hot melt (200 DEG C), in detail, by membranaceous PKHH plastics, it is affixed on 3K carbon cloth, then is coated with it with release paper.After first with 200 DEG C of preheatings 30 minutes, then through overheated roller wheel load, after cooling, i.e. obtain PKHH thermoplastics type's prepreg cloth, found that fibrous inside local presents dry yarn state, the most about only have 50% infiltration.Fig. 1 b), c), d) figure be respectively with embodiment 1,4,5 impregnation carbon fiber vertical section, its fiber is visually all to present (100%) infiltration completely.
Table 1, each embodiment and the plastic nature on the composite wood synthesized by comparative example
125℃2Colloid osmotic chromatograph is used to analyze3Differential Scanning Calorimeter analyser is used to analyze4Use thermal deformation
Temperature test machine is analyzed
Understand via the comparison of above example and comparative example, according to difunctionality base epoxy and monofunctional primary amine and/or the mixture of difunctionality base secondary amine sclerosing agent of the present invention；Owing to this mixture low temperature can be impregnated with less than 60 degree, therefore processing procedure is easier to；And due to the characteristic of mixture so that it is preferable with the composite interlayer associativity that fiber is formed；Therefore, the thermoplastic fibre composite of gained, can add different functionalities additive, and have the characteristics such as resistance to combustion, endurance, impact resistance, resistance to yellow, therefore can be applicable to multiple fields.
Claims (12)
1. the mixture of a difunctionality base epoxy and monofunctional primary amine and/or difunctionality base secondary amine sclerosing agent is as preimpregnation
The purposes of material, it carries out in-situ polymerization after impregnation one dispersion phase, forms thermoplastic composite.
2. purposes as claimed in claim 1, wherein in this difunctionality base epoxy, containing the asphalt mixtures modified by epoxy resin of one or more 60 to 100wt%
Lipoprotein mixture, and containing the functional interpolation auxiliary agent of 0～25wt%.
3. purposes as claimed in claim 1, wherein this difunctionality base epoxy is that epoxide equivalent (EEW) is between 50 to 650 persons.
4. purposes as claimed in claim 1, wherein this difunctionality base epoxy is for comprising arbitrary or mixing following formula (I) to (IV):
Wherein, X1Represent C4～C18Alkyl；N is 0～20；X2To X21Can be identical or different, and represent H, P, alkyl or halogen
Element；And Y represents S, O or C atom.
5. purposes as claimed in claim 1, wherein comprises in this monofunctional primary amine level/or difunctionality base secondary amine sclerosing agent
One or more than one functional group's primary amine levels/of 80～100wt% or difunctionality base secondary amine mixture, 0～10wt% functional add
Adding assistant.
6. such as the purposes of claim 2 or 5, the wherein choosing of this functional interpolation auxiliary agent free shrinking agent, flame retardant, ultraviolet resistance
The group that auxiliary agent, anti-wear agent and toughener are formed.
7. purposes as claimed in claim 1, wherein this monofunctional primary amine level/or difunctionality base secondary amine sclerosing agent for comprise arbitrary or
Mix following formula V to (VII):
Wherein, RaFor alkyl, aryl or aralkyl；RbFor alkyl or aryl；RcFor alkyl.
8. the method preparing thermoplastic composite, comprises: mixing difunctionality base epoxy and monofunctional primary amine and/or
Difunctionality base secondary amine sclerosing agent forms prepreg, and this mixture is impregnated with in-situ polymerization after a dispersion phase.
9. method as claimed in claim 8, wherein this prepreg impregnation dispersion phase is through hand lay-up, brushwork forming or priming by vacuum
Mode.
10. method as claimed in claim 8, when wherein this mixture is low-viscosity, prepreg impregnation dispersion phase is through drum type coiling method
(Drum Winding), filament winding process (Filament-Winding), pultrusion processes (Pultrusion), more heated carry out in situ
Polymerization.
11. methods as claimed in claim 8, when wherein this mixture is high viscosity, prepreg impregnation dispersion phase is through high temperature impregnation system
Journey (Hot-melt Impregnation) is impregnated with, more heated carries out in-situ polymerization.
12. 1 kinds of thermoplastic composites, it is that the method using claim 8 or 9 or 10 or 11 prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510217836.1A CN106117514A (en) | 2015-05-04 | 2015-05-04 | Difunctionality base epoxy and monofunctional primary amine and/or difunctionality base secondary amine hardener mixture are as the purposes of prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510217836.1A CN106117514A (en) | 2015-05-04 | 2015-05-04 | Difunctionality base epoxy and monofunctional primary amine and/or difunctionality base secondary amine hardener mixture are as the purposes of prepreg |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106117514A true CN106117514A (en) | 2016-11-16 |
Family
ID=57471444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510217836.1A Pending CN106117514A (en) | 2015-05-04 | 2015-05-04 | Difunctionality base epoxy and monofunctional primary amine and/or difunctionality base secondary amine hardener mixture are as the purposes of prepreg |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106117514A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467884A (en) * | 2018-11-07 | 2019-03-15 | 常州百思通复合材料有限公司 | A kind of thermoplastic polymer based composites and preparation method thereof |
| US11180622B2 (en) | 2018-11-07 | 2021-11-23 | Changzhou Bamstone Composites Co., Ltd. | Thermoplastic polymer-based composite material and preparation method thereof |
| CN114381247A (en) * | 2022-01-24 | 2022-04-22 | 西南石油大学 | Synthesis of branched epoxy resin pressure-bearing plugging material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1141935A (en) * | 1967-03-22 | 1969-02-05 | Dow Chemical Co | A process for preparing a linear epoxy resin |
| CN1732213A (en) * | 2002-12-27 | 2006-02-08 | 日东纺绩株式会社 | Method for producing fiber-reinforced thermoplastic plastic and fiber-reinforced thermoplastic prastic |
| CN102272191A (en) * | 2009-01-09 | 2011-12-07 | 长濑化成株式会社 | Process for production of thermoplastic cured epoxy resin with transparency to visible light, and thermoplastic epoxy resin composition |
-
2015
- 2015-05-04 CN CN201510217836.1A patent/CN106117514A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1141935A (en) * | 1967-03-22 | 1969-02-05 | Dow Chemical Co | A process for preparing a linear epoxy resin |
| CN1732213A (en) * | 2002-12-27 | 2006-02-08 | 日东纺绩株式会社 | Method for producing fiber-reinforced thermoplastic plastic and fiber-reinforced thermoplastic prastic |
| CN102272191A (en) * | 2009-01-09 | 2011-12-07 | 长濑化成株式会社 | Process for production of thermoplastic cured epoxy resin with transparency to visible light, and thermoplastic epoxy resin composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467884A (en) * | 2018-11-07 | 2019-03-15 | 常州百思通复合材料有限公司 | A kind of thermoplastic polymer based composites and preparation method thereof |
| WO2020093438A1 (en) * | 2018-11-07 | 2020-05-14 | 常州百思通复合材料有限公司 | Thermoplastic polymer-based composite material and preparation method therefor |
| US11180622B2 (en) | 2018-11-07 | 2021-11-23 | Changzhou Bamstone Composites Co., Ltd. | Thermoplastic polymer-based composite material and preparation method thereof |
| US11505664B2 (en) | 2018-11-07 | 2022-11-22 | Changzhou Bamstone Composites Co., Ltd. | Thermoplastic polymer-based composite material and preparation method thereof |
| CN114381247A (en) * | 2022-01-24 | 2022-04-22 | 西南石油大学 | Synthesis of branched epoxy resin pressure-bearing plugging material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104781303B (en) | Epoxy-resin systems for the tetramine containing polyethylene of resin transfer moulding method | |
| EP3149065B1 (en) | Thermomechanically reprocessable epoxy composites and processes for their manufacturing | |
| CA2769296C (en) | Coated reinforcement | |
| CN103857731A (en) | Fiber-reinforced resin composite material and process for producing same | |
| CN101945944A (en) | Epoxy resin composition, fiber-reinforced composite material and method for producing the same | |
| US20160152822A1 (en) | 1k thermoset epoxy composition | |
| US9303131B2 (en) | Premolding article from thermoset and thermoplastic polymer dispersions | |
| WO2015079917A1 (en) | Reinforcing fiber fabric substrate, preform, and fiber-reinforced composite material | |
| CN107708954A (en) | Improvement or the improvement relevant with three dimensional molded part in three dimensional molded part | |
| CN107108827A (en) | Benzoxazine and the composition containing benzoxazine | |
| KR102361346B1 (en) | Epoxy resin composition for fiber-reinforced composite material, and fiber-reinforced composite material | |
| CN106117514A (en) | Difunctionality base epoxy and monofunctional primary amine and/or difunctionality base secondary amine hardener mixture are as the purposes of prepreg | |
| TWI815628B (en) | Carbon fiber bundles, prepregs, fiber reinforced composites | |
| JP6655021B2 (en) | Epoxy resin type | |
| CN110202905A (en) | In-situ three-dimensional resin composite materials and its application | |
| JP2002522257A (en) | Resin transfer molding | |
| JP6609304B2 (en) | Epoxy system using triethylamine tetraamine and tin catalyst | |
| TWI610974B (en) | Use of a mixture of difunctional epoxy with monofunctional primary amine compound and/or difunctional secondary amine curing agent; composites comprising the mixture and the manufacture method thereof | |
| US11180622B2 (en) | Thermoplastic polymer-based composite material and preparation method thereof | |
| US20230212356A1 (en) | Sulfur-containing material and use thereof | |
| JP6493633B1 (en) | Thermosetting resin composition for fiber reinforced composite material, preform, fiber reinforced composite material and method for producing fiber reinforced composite material | |
| CN106566099A (en) | Carbon fiber reinforced thermoplastic resin composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161116 |
|
| RJ01 | Rejection of invention patent application after publication |